Polymerizable composition and molded articles produced by using the same

ABSTRACT

The present invention provides a polymerizable composition and a resin formed object capable of providing a crosslinked cycloolefin resin formed object and a crosslinked cycloolefin resin composite excellent in heat resistance, more specifically, a polymerizable composition comprising a cycloolefin mixture containing 0.1 to 50 % by mole of a cycloolefin having, as a substituent group, a monovalent group including an aliphatic carbon-carbon unsaturated bond, a metathesis polymerization catalyst, and a radical generating agent; and formed objects produced by using a polymerizable composition described above which preferably further comprises a chain transfer agent and making the cycloolefin mixture undergo at least ring-opening polymenzation.

TECHNICAL FIELD

The invention relates to a polymerizable composition containingcycloolefin and a resin formed object produced by using the same, and inparticular, to a polymerizable composition and a resin formed objectthat can provide a crosslinked resin formed object and a crosslinkedresin composite produced with cycloolefin resin excellent in heatresistance.

BACKGROUND ART

It has been known that a crosslinked resin formed object is obtained bycrosslinking, with a crosslinking agent such as an organic peroxide orthe like, a cycloolefin resin obtained by ring-opening polymerizing acycloolefin such as norbornene in the presence of a metathesispolymerization catalyst. It is known that the crosslinked resin formedobject is excellent in electric characteristics such as a low dielectricconstant and a low dielectric loss tangent in addition to a mechanicalstrength and a chemical resistance. Focusing on these characteristics, afilm-shaped resin formed object has been manufactured, for example, bycasting a solution obtained by dissolving a cycloolefin polymer and acrosslinking agent into a solvent onto a flat plate, and thenevaporating the solvent by heat at the same time crosslinking. Further,a proposal that the film-shaped resin formed object obtained islaminated with a substrate for printed wiring board or the like toproduce a crosslinked resin composite used for electronic parts has beensuggested. In Japanese Patent Application Laid-Open No. 6-248164,disclosed are: a film obtained by casting a norbornene resin compositionobtained by dissolving a thermoplastic hydrogenated ring-openingnorbornene resin, an organic peroxide and a crosslinking agent into asolvent onto a supporting body and then drying; and a crosslinked resincomposite obtained by pressing, heating and crosslinking the laminate ofa copper foil and a prepreg obtained by impregnating a fiberreinforcement with the above norbornene resin composition and thendrying. However, the crosslinked resin composite obtained by abovemethod does not have a sufficient heat resistance enough to produceelectronic parts by using a lead-free solder that has been adopted as anenvironmental protection. Further, there is a problem that the processis complicated because it is necessary to remove a solvent to obtain afilm-shaped crosslinked resin formed object. To solve the problem, inJapanese Patent Application National Publication No. 11-507962, proposedis a method for obtaining a crosslinked resin by producing a cycloolefinpolymer by ring-opening polymerizing a cycloolefin without a solvent inthe presence of a ruthenium carbene complex and a peroxide, and thenconducting post-curing (or post-crosslinking).

DISCLOSURE OF INVENTION

As a result of studies having been conducted by the present inventor, ithas been found that a crosslinked resin obtained by the method describedin Japanese Patent Application National Publication No. 11-507962 doesnot have a sufficient heat resistance in some case.

Accordingly, it is an object of the present invention, which has beenmade in light of the problems of the conventional technology, to providea polymerizable composition and a resin formed object capable ofproviding a crosslinked cycloolefin resin formed object and acrosslinked cycloolefin resin composite excellent in heat resistance.

The present inventor has repeated extensive researches in order to solvethe above problems so as to find out that the heat resistance of a resinformed object, a crosslinked resin formed object and a crosslinked resincomposite obtained can be improved by controlling a kind and an amountof crosslinking sites which react with a radial generator in aring-opening polymer of cycloolefin. Besides, the present inventor hasfound that the object is achieved by using a cycloolefin with a specificchemical structure in a specific ratio together with a metathesispolymerization catalyst and a radical generating agent. Based on suchfindings and knowledge, the invention has been completed.

According to this invention, the following first to eighth aspectsthereof will be provided.

-   1. A polymerizable composition comprising: a cycloolefin mixture    containing 0.1 to 50% by mole of a cycloolefin having, as a    substituent group, a monovalent group including an aliphatic    carbon-carbon unsaturated bond, a metathesis polymerization catalyst    and a radical generating agent.-   2. The polymerizable composition according to above 1, further    comprising a chain transfer agent.-   3. A resin formed object obtained by ring-opening polymerizing the    polymerizable composition as in above 1 or 2.-   4. A resin formed object obtained by applying the polymerizable    composition as in above 1 on a supporting body, followed by    ring-opening polymerizing the polymerizable composition applied.-   5. A resin formed object obtained by injecting the polymerizable    composition as in above 1 into a cavity of a mold, followed by    ring-opening polymerizing the polymerizable composition injected.-   6. A resin formed object obtained by impregnating a fiber    reinforcement with the polymerizable composition as in above 1,    followed by ring-opening polymerizing the polymerizable composition    impregnated.-   7. A crosslinked resin formed object obtained by heating and    crosslinking the resin formed object as in above 3 to the    temperature higher than the peak temperature during the ring-opening    polymerization.-   8. A crosslinked resin composite obtained by laminating the resin    formed object as in above 3 with a base material, followed by    heating and crosslinking the laminate.

The present invention provides a polymerizable composition and a resinformed object capable of providing a crosslinked cycloolefin resinformed object and a crosslinked cycloolefin resin composite excellent inheat resistance.

BEST MODE FOR CARRYING OUT THE INVENTION

A polymerizable composition of this invention comprises; a cycloolefinmixture containing 0.1 to 50% by mole of a cycloolefin having, as asubstituent group, a monovalent group including an aliphaticcarbon-carbon unsaturated bond (the cycloolefin is also hereafterreferred to as a “specific cycloolefin”), a metathesis polymerizationcatalyst and a radical generating agent.

The specific cycloolefin used in this invention is the cycloolefin inwhich, as a substituent group, a monovalent group including an aliphaticcarbon-carbon unsaturated bond is bonded to a monocyclic or polycyclicaliphatic hydrocarbon having a carbon-carbon double bond in the ring.

Any monovalent groups each including an aliphatic carbon-carbonunsaturated bond can be used as far as they have an aliphaticcarbon-carbon unsaturated bond. The monovalent group has usually 2 to 30carbon atoms and preferably 2 to 20 carbon atoms. The unsaturated bondis preferably a carbon-carbon double bond. Besides, the carbon-carbonunsaturated bond preferably exists in an a cyclic hydrocarbon group.Further, the carbon-carbon unsaturated bond preferably exists at theterminal of the atomic group. The monovalent group including analiphatic carbon-carbon unsaturated bond may have a substituent groupincluding a heteroatom.

Examples of the monovalent group including an aliphatic carbon-carbonunsaturated bond include a vinyl group, an allyl group, an acryloylgroup, a methacryloyl group, a vinyloxy group, an allyloxy group, avinyloxycarbonyl group, an allyloxycarbonyl group, an acryloxymethylgroup, a methacryloxymethyl group, a vinylphenyl group, apropenoxycarbonylphenyloxycarbonyl group and the like.

The specific cycloolefin is incorporated to a polymer by ring-openingmetathesis polymerization of the cycloolefin ring thereof. When thecrosslinking reaction is conducted in the polymers by a radicalgenerating agent described later, the unsaturated bond portion of theatomic group in the polymer acts as a crosslinking point and thecrosslinking reaction proceeds. Therefore, a crosslinked resin formedobject with a high crosslinking density can be formed.

The cycloolefin mixture usually contains the specific cycloolefin in therange of 0.1 to 50% by mole, preferably 0.5 to 40% by mole and morepreferably 1 to 30% by mole. When the amount of the specific cycloolefinis too small, the crosslinking density may lower and thus sufficientheat resistance cannot be obtained, while when the amount of thespecific cycloolefin is too large, mechanical properties of the resinformed object may lower.

Examples of the specific cycloolefin include monocycloolefin compoundssuch as 3-vinyl-1-cyclobutene, 3-vinyl-1-cyclopentene,3-vinyl-1-cyclohexene, 4-vinyl-1-cyclohexene,3-methyl-5-vinyl-1-cyclohexene, allyl 3-cyclohexene-1-carboxylate, vinyl3-cyclohexene-1-carboxylate and allyl1-methyl-3-cyclohexene-1-carboxylate;

bicycloolefin compounds such as 5-vinyl-2-norbornene,5-(2-propenyl)-2-norbornene, 5-(3-butenyl)-2-norbornene,5-(4-pentenyl)-2-norbornene, 5,6-divinyl-2-norbornene,5-methyl-6-vinyl-2-norbornene, 5-vinyloxy-2-norbornene,5-vinyloxymethyl-2-norbornene, 5-allyloxy-2-norbornene,5-allyloxymethyl-2-norbornene, vinyl 2-norbornene-5-carboxylate, allyl2-norbornene-5-carboxylate, 4-vinylphenyl 2-norbornene-5-carboxylate,vinyl 5-methyl-2-norbornene-5-carboxylate, allyl5-methyl-2-norbornene-5-carboxylate, 4-vinylphenyl5-methyl-2-norbornene-5-carboxylate, 5-norbornen-2-yl methacrylate,5-norbornen-2-yl acrylate, 5-norbornen-2-ylmethyl methacrylate,5-norbornen-2-ylmethyl acrylate, divinyl2-norbornene-5,6-dicarbonxylate, diallyl2-norbornene-5,6-dicarbonxylate, vinyl6-methoxycarbonyl-2-norbornene-5-carboxylate, allyl6-methoxycarbonyl-2-norbornene-5-carboxylate, vinyl6-ethoxycarbonyl-2-norbornene-5-carboxylate, allyl6-ethoxycarbonyl-2-norbornene-5-carboxylate, 2-acryloxyethyl2-norbornene-5-carboxylate, 2-methacryloxyethyl2-norbornene-5-carboxylate, 5-norbornen-2-ylmethyl2-(2-propenoxycarbonyl)benzoate, 2,2-di(acryloxymethyl)pentan-4-yl2-norbornene-5-carboxylate, 2,2-di(methacryloxymethyl)pentan-4-yl5-methyl-2-norbornene-5-carboxylate and 7-oxa-5-norbornen-2-ylmethacrylate;

tricycloolefin compounds such asN-(4-vinylphenyl)-2-norbornene-5,6-dicarboxyimide,N-allyl-2-norbornene-5,6-dicarboxyimide,9-vinyltricyclo[6.2.1.0^(2,7)]undec-4-ene and4-vinyltricyclo[6.2.1.0^(2,7)]undec-9-ene; and

tetracycloolefin compounds such as 9-vinyl-4-tetracyclododecene,9-(2-propenyl)-4-tetracyclododecene, vinyl4-tetracyclododecene-9-carboxylate, allyl4-tetracyclododecene-9-carboxylate and diallyl4-tetracyclododecene-9,10-dicarboxylate.

The cycloolefin mixture may contain other cycloolefin than the specificcycloolefin. As the cycloolefin other than the specific cycloolefin, acycloolefin monomer having no monovalent group including an aliphaticcarbon-carbon unsaturated bond (the norbornene monomer and themonocycloolefin monomer) can be used together with the specificcycloolefin.

Examples of the norbornene monomer include norbornenes,dicyclopentadienes, tetracyclododecenes and penta- or more-cycloolefins.The norbornene monomer may have a hydrocarbon group such as methyl groupor a polar group such as carboxyl group.

Specific examples of norbornenes include bicyclo[2.2.1]hept-2-ene(hereinafter referred to as 2-norbornene), 5-methyl-2-norbornene,5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene,5-decyl-2-norbornene, 5-cyclohexyl-2-norbornene,5-cyclopentyl-2-norbornene, 5-ethylidene-2-norbornene,5-cyclohexenyl-2-norbornene, 5-cyclopentenyl-2-norbornene,5-phenyl-2-norbornene,tetracyclo[9.2.1.0^(2,10).0^(3,8)]tetradeca-3,5,7,12-tetraene (alsoreferred to as 1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene),tetracyclo[10.2.1.0^(2,11).0^(4,9)]pentadeca-4,6,8,13-tetraene (alsoreferred to as 1,4-methano-1,4,4a,9,9a,10-hexahydroanthracene), methyl2-norbornene-5-carboxylate, ethyl 2-norbornene-5-carboxylate, methyl5-methyl-2-norbornene-5-carboxylate, ethyl5-methyl-2-norbornene-5-carboxylate, 5-norbornen-2-yl acetate,2-methyl-5-norbornen-2-yl acetate, 5-norbornen-2-yl acrylate,2-norbornene-5-carboxylic acid, 2-norbornene-5,6-dicarboxylic acid,2-norbornene-5,6-dicarboxylic anhydride, 2-norbornene-5-methanol,2-norbornene-5,6-dimethanol, 2-norbornen-5-ol,2-norbornene-5-carbonitrile, 2-norbornene-5-carbaldehyde,2-norbornene-5-carboxamide, 5-acetyl-2-norbornene,6-methoxycarbonyl-2-norbornene-5-carboxylic acid,2-norbornene-5,6-dicarboxyimide,

7-oxa-2-norbornene, 5-methyl-7-oxa-2-norbornene,5-ethyl-7-oxa-2-norbornene, 5-butyl-7-oxa-2-norbornene,5-hexyl-7-oxa-2-norbornene, 5-cyclohexyl-7-oxa-2-norbornene,5-ethylidene-7-oxa-2-norbornene, 5-phenyl-7-oxa-2-norbornene, methyl7-oxa-2-norbornene-5-carboxylate and 7-oxa-5-norbornen-2-yl acetate.

Specific examples of dicyclopentadienes include dicyclopentadiene,methyldicyclopentadiene,dihydrodicyclopentadiene(tricyclo[5.2.1.0^(2,6)]dec-8-ene) and the like.

Specific examples of tetracyclododecenes includetetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene (hereinafter referred to as4-tetracyclododecene), 9-methyl-4-tetracyclododecene,9-ethyl-4-tetracyclododecene, 9-cyclohexyl-4-tetracyclododecene,9-cyclopentyl-4-tetracyclododecene, 9-methylene-4-tetracyclododecene,9-ethylidene-4-tetracyclododecene, 9-cyclohexenyl-4-tetracyclododecene,9-cyclopentenyl-4-tetracyclododecene, 9-phenyl-4-tetracyclododecene,methyl 4-tetracyclododecene-9-carboxylate, methyl9-methyl-4-tetracyclododecene-9-carboxylate,4-tetracyclododecene-9-methanol, 4-tetracyclododecen-9-ol,4-tetracyclododecene-9-carboxylic acid,4-tetracyclododecene-8,9-dicarboxyic acid,4-tetracyclododecene-8,9-dicarboxylic anhydride,4-tetracyclododecene-9-carbonitrile,4-tetracyclododecene-9-carbaldehyde, 4-tetracyclododecene-9-caboxamide,4-tetracyclododecene-8,9-dicarboxyimide, 9-chloro-4-tetracyclododecene,9-trimethoxysilyl-4-tetracyclododecene and9-acetyl-4-tetracyclododecene.

Specific examples of penta- or more-cycloolefins includepentacyclo[6.5.1.1^(3,6).0^(2,7).0^(9,13)]pentadeca-4,10-diene,pentacyclo[9.2.1.1^(4,7).0^(2,10).0^(3,8)]pentadeca-5,12-diene andhexacyclo[6.6.1.1^(3,6).1^(10,13).0^(2,7).0^(9,14)]heptadec-4-ene.

These norbornene monomers can be used as one kind alone, but also usedas two or more kinds together. By using two or more kinds of themtogether and varying the blending ratio, it is possible to control aglass transition temperature and a melting point of the formed object tobe obtained.

Examples of the monocycloolefin monomer include cyclobutene,cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, andderivatives thereof each having a polar group such as a carboxyl group.

When the monocycloolefin monomer is used, the cycloolefin mixturecontains the monocycloolefin monomer preferably 40% by weight or lessand more preferably 20% by weight or less. When the amount of themonocycloolefin monomer is too large, the polymer obtained byring-opening polymerization tends to be not in the state of a resin, butin the state of an elastomer.

The metathesis polymerization catalyst used in this invention is notparticularly limited insofar as it enables the ring-opening metathesispolymerization of the cycloolefin monomer. An example of the metathesispolymerization catalyst is a complex having a transition metal atom as acentral atom to which a plurality of ions, atoms, multi-atom ions and/orcompounds are bonded. Examples of the transition metal atoms include:atoms of groups 5, 6 and 8 of a periodic table (long periodic-type,which also applies in later description). The atom in respective groupsis not particularly limited, and the examples thereof are tantalum inGroup 5, molybdenum or tungsten in Group 6 and ruthenium or osmium inGroup 8.

Among them, preferable is the complex of ruthenium or osmium in group 8and, for the following reason, more preferable is a ruthenium carbenecomplex in which a carbene is coordinated to a ruthenium atom. Theruthenium carbene complex is excellent in catalytic activity, thus makesthe reaction conversion of ring-opening polymerization high, andtherefore is excellent in productivity of the resin formed object.Besides, the resin formed object to be obtained is less smelly(originating from unreacted cyclic olefin). Further, the rutheniumcarbene complex is relatively stable to oxygen and water in air andhardly inactivated.

The ruthenium complex catalyst can be produced by methods described in,for example, Organic Letters., vol. 1, p. 953 (1999) and TetrahedronLetters., vol. 40, p. 2247 (1999).

Examples of the ruthenium carbene complex include ruthenium complexcompounds in which a heteroatom-containing carbene compound and aneutral electron-donating compound are bonded to a ruthenium atom, suchas benzylidene (1,3-dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesitylimidazolidin-2-ylidene)(3-methyl-2-buten-1-ylidene) (tricyclopentyl phosphine) rutheniumdichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene)(tricyclohexyl phosphine) ruthenium dichloride, benzylidene(1,3-di(1-phenylethyl)-4-imidazolin-2-ylidene) (tricyclohexyl phosphine)ruthenium dichloride, benzylidene(1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexyl phosphine)(1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazol-5-ylidene)ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene)(ethoxymethylene) (tricyclohexyl phosphine) ruthenium dichloride, andbenzylidene (1,3-dimesitylimidazolidin-2-ylidene) pyridine rutheniumdichloride;

ruthenium complex compounds in which two heteroatom-containing carbenecompounds are bonded to a ruthenium atom, such asbenzylidenebis(1,3-dicyclohexylimidazolidin-2-ylidene) rutheniumdichloride and benzylidenebis(1,3-diisopropyl-4-imidazolin-2-ylidene)ruthenium dichloride; and

other ruthenium compounds such as (1,3-dimesitylimidazolidin-2-ylidene)(phenylvinylidene) (tricyclohexyl phosphine) ruthenium dichloride,(t-butylvinylidene) (1,3-diisopropyl-4-imidazolin-2-ylidene)(tricyclopentyl phosphine) ruthenium dichloride, andbis(1,3-dicyclohexyl-4-imidazolin-2-ylidene)phenyl vinylidene rutheniumdichloride.

The amount of the metathesis polymerization catalyst, in terms of themolar ratio of (transition metal atom in the catalyst cycloolefinmixture), is usually in the range of 1:2,000 to 1:2,000,000, preferably1:5,000 to 1:1,000,000, more preferably 1:10,000 to 1:500,000.

The radical generating agent used in this invention is a compound whichgenerates a radical by heating and has effect on crosslinking thecycloolefin polymer with the radical. The site where the radicalgenerating agent causes the crosslinking reaction is mainly acarbon-carbon double bond in the resin constituting the resin formedobject, but in some case, crosslinking is caused in a saturated bondportion in the resin.

Examples of the radical generating agent include an organic peroxide anda diazo compound. Examples of the organic peroxide includehydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxideand cumene hydroperoxide; dialkyl peroxides such as dicumyl peroxide andt-butyl cumyl peroxide; diacyl peroxides such as dipropionyl peroxideand benzoyl peroxide; peroxyketals such as2,5-dimethyl-2,5-di(t-butylperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3 and1,3-di(t-butylperoxyisopropyl)benzene; peroxyesters such ast-butylperoxyacetate and t-butylperoxybenzoate; peroxycarbonates such ast-butylperoxyisopropyl carbonate and di(isopropylperoxy) dicarbonate;and alkylsilyl peroxides such as t-butyl trimethylsilyl peroxide. Amongthem, preferably are dialkyl peroxides since the hindrance against themetathesis polymerization reaction in the bulk polymerization is lower.

Examples of the diazo compound include4,4′-bisazidobenzal(4-methyl)cyclohexanone, 4,4′-diazidochalcone,2,6-bis(4′-azidobenzal)cyclohexanone,2,6-bis(4′-azidobenzal)-4-methylcyclohexanone, 4,4′-diazidophenylsulfon,4,4′-diazidodiphenylmethane and 2,2′-diazidostilbene.

The amount of the radical generating agent is usually in the range of0.1 to 10 parts by weight and preferably 0.5 to 5 parts by weight per100 parts by weight of the cycloolefin mixture. When the amount of theradical generating agent is too small, crosslinking may be insufficientand the crosslinked resin formed object with a high crosslinking densitymay not be obtained. To the contrary, when the amount of the radicalgenerating agent is too large, the crosslinking effect is saturated andthus the crosslinked resin formed object with a desired physicalproperties may not be obtained.

Various kinds of additives can be if necessary incorporated into thepolymerizable composition of this invention in the range where theadditive does not hinder the effect of this invention. Examples thereofinclude a chain transfer agent, an activator (cocatalyst), apolymerization retarder, a crosslinking assistant, a filler, a solvent,a modifier, an antioxidant, a flame retardant, a colorant, a lightstabilizer and the like.

By adding the chain transfer agent into the polymerizable composition ofthis invention, the progress of the crosslinking reaction due to theheat generated in ring-opening polymerization can be prevented. Theresin formed object obtained by ring-opening polymerization of thepolymerizable composition containing the chain transfer agent comes tomolten-state by heating at a high temperature, and when the temperaturethereof reaches to the temperature higher than the maximum temperature(peak temperature) during the ring-opening polymerization, thecrosslinking reaction gets to progress therein to provide thecrosslinked resin formed object.

When the resin formed object is laminated with a base material such as ametal foil and thereafter the laminate is heated, the molten-state resinformed object deforms in accordance with the shape of the base material,and therefore the adherence in the interface therebetween improvesremarkably.

Specific examples the chain transfer agent include aliphatic olefinssuch as 1-hexene and 2-hexene; aromatic olefins such as styrene,vinylstyrene, stilbene, vinylbenzene and divinylbenzene; vinyl alicycliccompounds such as vinylcyclohexane; vinyl ethers such as ethyl vinylether and allyl glycidyl ether; vinyl ketones such as methyl vinylketones; ethylenically unsaturated esters such as allyl acetate andallyl methacrylate; alcoxy silanes such as vinyl trimethoxy silane,allyl trimethoxy silane and p-styryl trimethoxy silane; hydrocarbonchain transfer agents each having two or more vinyl groups such as1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene,3,3-dimethyl-1,4-pentadiene, 3,5-dimethyl-1,6-heptadiene,3,5-dimethoxy-1,6-heptadiene, 1,2-divinylcyclohexane,1,3-divinylcyclohexane, 1,4-divinylcyclohexane, 1,2-divinylbenzene,1,3-divinylbenzene, 1,4-divinylbenzene, divinyl cyclopentane, diallylbenzene, divinyl naphthalene, divinyl anthracene, divinyl phenanthrene,trivinylbenzene, and polybutadiene (including 1,2-addition ratio 10% ormore); and heteroatom-containing chain transfer agents each having twoor more vinyl groups such as diallyl ether, 1,5-hexadien-3-on, diallylmaleate, diallyl oxalate, diallyl malonate, diallyl succinate,diallylglutarate, diallyladipate, diallylphthalate, diallyl fumalate,diallyl terephthalate, triallyl cyanurate, triallyl isocianurate,divinyl ether, allyl vinyl ether, divinyl maleate, divinyl oxalate,divinyl malonate, divinyl succinate, divinyl glutarate, divinyl adipate,divinyl phthalate, divinyl fumalate, divinyl terephthalate, trivinylcyanurate and trivinyl isocyanurate. The amount of the chain transferagent is usually in the range of 0.01 to 10 parts by weight, preferably0.05 to 5 parts by weight, and more preferably 0.1 to 2 parts by weightper 100 parts by weight of the cycloolefin mixture. When the amount ofthe chain transfer agent is in the range, the resin formed objectexcellent in fluidity can be obtained since the crosslinking reactionduring the ring-opening polymerization is sufficiently suppressed.

Among the hydrocarbon chain transfer agents each having two or morevinyl groups in the molecule, when the hydrocarbon chain transfer agenthaving no heteroatom such as oxygen, nitrogen, or sulfur in the moleculeis used, the crosslinked resin formed object or the crosslinked resincomposite of this invention acquires the low electric characteristicssuch as specific inductive capacity and dielectric loss tangent andtherefore is preferably used as an electric insulating material for ahigh frequency signal. Other chain transfer agent other than the abovecompound having two or more vinyl groups in the molecule can be usedtogether therewith. Example of the other chain transfer agent is acompound having only one vinyl group. The amount of the chain transferagent having only one vinyl group in the molecule is usually 50% by moleor less, preferably 40% by mole or less, more preferably 30% by mole orless and especially preferably 10% by mole or less per the amount of thechain transfer agent having two or more vinyl groups in the molecule.

The activator (cocatalyst) or the polymerization retarder can be addedinto the polymerizable composition for the purpose of controlling thepolymerization activity of the metathesis polymerization catalyst orimproving the polymerization reaction conversion. The activator can beexemplified by (partial) alkylation products, (partial) halogenationproducts, (partial) alkoxylation products and (partial) aryloxylationproducts of aluminum, scandium, tin, titanium, and zirconium

Specific examples of the activator include trialkoxy aluminum,triphenoxy aluminum, dialkoxyalkyl aluminum, alkoxydialkyl aluminum,trialkyl aluminum, dialkoxy aluminum chloride, alkoxyalkyl aluminumchloride, dialkyl aluminum chloride, trialkoxyscandium, tetraalkoxytitanium, tetraalkoxy tin, and tetraalkoxy zirconium.

Examples of the polymerization retarder include acyclic diene compoundssuch as 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene,(cis,cis)-2,6-octadiene (cis,trans)-2,6-octadiene and(trans,trans)-2,6-octadiene; acyclic triene compounds such as(trans)-1,3,5-hexatriene, (cis)-1,3,5-hexatriene,(trans)-2,5-dimethyl-1,3,5-hexatriene and(cis)-2,5-dimethyl-1,3,5-hexatriene; phosphines such astriphenylphosphine, tri-n-butylphosphine and methyldiphenylphosphine;and Lewis bases such as aniline.

A cycloolefin having a diene structure or a triene structure in the ringcan be used as the polymerization retarder. Examples of the cycloolefininclude monocycloolefins such as 1,5-cyclooctadiene,1,5-dimethyl-1,5-cyclooctadiene, 1,3,5-cycloheptatriene and(cis,trans,trans)-1,5,9-cyclododecatriene. Since the cycloolefin havinga diene structure or a triene structure in the ring is thepolymerization retarder and at the same time the cycloolefin, thecycloolefin can be used as part of the cycloolefin mixture.

The amount of the activator or the polymerization retarder can be setarbitrarily depending on the used compound and the object, and usuallyin the range of 1:0.05 to 1:100, preferably 1:0.2 to 1:20 and morepreferably 1:0.5 to 1:10, in terms of the molar ratio of (transitionmetal atom in the metathesis polymerization catalyst:the activator orthe polymerization retarder).

The crosslinking assistant can be added into the polymerizablecomposition for the purpose of improving the crosslinking reaction rate.Examples of the crosslinking assistant include dioxime compounds such asp-quinone dioxime; methacrylate compounds such as lauryl methacrylateand trimethylolpropane trimethacrylate; fumaric acid compounds such asdiallyl fumarate; phthalic acid compounds such as diallyl phthalate;cyanuric acid compounds such as tryallyl cyanurate; and imide compoundssuch as maleimide. The amount of the crosslinking assistant is notparticularly limited, but is usually in the range of 0 to 100 parts byweight and preferably 0 to 50 parts by weight per 100 parts by weight ofthe cycloolefin mixture.

The filler can be added into the polymerizable composition for thepurpose of reducing linear expansion coefficient, improving mechanicalstrength such as elastic modulus, increasing dielectric constant,decreasing dielectric loss tangent and decreasing the degree ofshrinkage on curing of the resin formed object, the crosslinked resinformed object and the crosslinked resin composite obtained byring-opening polymerization of the polymerizable composition.

The filler is preferably in a particulate form. The average particlediameter determined by measuring the lengths of the major axes of 1000filler particles under a scanning electron microscope is preferably inthe range of 0.001 to 100 μm, more preferably 0.01 to 50 μm, still morepreferably 0.1 to 20 μm.

The filler may be an inorganic filler or an organic filler, and in orderto achieve the above object, the inorganic filler is preferable.Examples of the inorganic filler include hydroxides such as aluminumhydroxide, magnesium hydroxide and calcium hydroxide; oxides such assilicon oxide (silica), aluminum oxide and zinc oxide; chlorides such assodium chloride and calcium chloride; sulfates such as sodium hydrogensulfate and sodium sulfate; nitrates such as sodium nitrate and calciumnitrate; phosphates such as sodium dihydrogen phosphate and sodiumhydrogen phosphate; silicates such as mica, kaolin, fly ash and talc;titanates such as barium titanate and calcium titanate; carbides such assilicon carbide and boron carbide; nitrides such as aluminum nitride,boron nitride and silicon nitride; glass powder; carbon black; particlesof metals such as aluminum, nickel, magnesium, copper, zinc and iron;ferrites such as Mn—Mg—Zn ferrite, Ni—Zn ferrite and Mn—Zn ferrite;powder of ferromagnetic metals such as carbonyl iron, iron-siliconalloy, iron-aluminum-silicon alloy and iron-nickel alloy. Among theabove fillers, preferable are hydroxides, oxides, titanates andcarbonates, and more preferable are aluminum hydroxide and magnesiumhydroxide among the hydroxides, silicon oxide (silica) among the oxides,barium titanate and calcium titanate among the titanates, and calciumcarbonate among the carbonates.

These fillers treated surface thereof with a silane coupling agent, atitanate coupling agent, an aluminum coupling agent or the like can alsobe used.

The amount of the filler is usually in the range of 1 to 1,000 parts byweight, preferably 100 to 900 parts by weight, more preferably 200 to800 parts by weight, and especially preferably 300 to 700 parts byweight per 100 parts by weight of the cycloolefin mixture. When theamount of the filler is too small, the purpose of reducing linearexpansion coefficient and improving mechanical strength of the resinformed object can not be completed sufficiently, while when the amountof the filler is too large, mechanical strength of the resin formedobject may lower.

By adding the radical crosslinking retarder in the polymerizablecomposition, fluidity and storage stability of the resin formed objectcan be improved, which is preferable.

Examples of the radical crosslinking retarder include hydroxyanisolessuch as 3-t-butyl-4-hydroxyanisole, 2-t-butyl-4-hydroxyanisole,3,5-di-t-butyl-4-hydroxyanisole, 2,5-di-t-butyl-4-hydroxyanisole,bis-1,2-(3,5-di-t-butyl-4-hydroxyphenoxy)ethane; dialkoxyphenols such as2,6-dimethoxy-4-methylphenol and 2,4-dimethoxy-6-t-butylphenol;catechols such as catechol, 4-t-butyl catechol and 3,5-di-t-butylcatechol; and benzoquinones such as benzoquinone, naphthoquinone andmethylbenzoquinone. Among them, hydroxyanisoles, catechols andbenzoquinones are preferable and hydroxyanisoles are more preferable.

The amount the radical crosslinking retarder contained is usually in therange of 0.001 to 1 mole and preferably 0.01 to 1 mole per one mole ofthe radical generating agent.

A small amount of the solvent is used to dissolve the metathesispolymerization catalyst or the radical generating agent if necessary.Also, the solvent can be used as the medium in solution polymerizationof the polymerizable composition. In both cases, the solvent should beinert to the catalyst. Examples of the solvent include acylic aliphatichydrocarbons such as n-pentane, n-hexane and n-heptane; alicyclichydrocarbons such as cyclopentane, cyclohexane, methyl cyclohexane,dimethyl cyclohexane, hexahydroindene and cyclooctane; aromatichydrocarbons such as benzene, toluene and xylene; nitrogen-containinghydrocarbons such as nitromethane, nitrobenzene and acetonitrile; andoxygen-containing hydrocarbons such as diethyl ether andtetrahydrofuran. Among them, preferable are aromatic hydrocarbons,acyclic aliphatic hydrocarbons and alicyclic hydrocarbons, which areexcellent in dissolubility of the catalyst and generally used inindustries. Further, a liquid antioxidant, a liquid plasticizer or aliquid modifier may be used as the solvent as far as it dose not degradethe activity of the metathesis polymerization catalyst.

Examples of the modifier include elastomers such as natural rubber,polybutadiene, polyisoprene, styrene-butadiene copolymer,styrene-butadiene-styrene block copolymer, styrene-isoprene-styrenecopolymer, acrylonitrile-butadiene-styrene copolymer,acrylonitrile-butadiene copolymer, ethylene-propylene-diene terpolymer,ethylene-vinyl acetate copolymer, polysufide synthetic rubber, acrylicrubber, urethane rubber, fluororubber, silicone rubber, polyesterelastomer, polyolefin thermoplastic elastomer and polyvinyl chloridethermoplastic elastomer.

Examples of the antioxidant include various kinds of antioxidants forplastics and rubbers such as a phenol type, a phosphorus type, an aminetype and the like. These antioxidants may be used either alone or incombination of two or more kinds.

The polymerizable composition of this invention is obtained by mixingthe cycloolefin mixture containing 0.1 to 50% by mole of the cycloolefinhaving, as the substituent group, the monovalent group including analiphatic carbon-carbon unsaturated bond, the metathesis polymerizationcatalyst and the radical generating agent, and preferably the chaintransfer agent, and if necessary the above additives. The apparatus,means and procedure for mixing the polymerizable composition are notparticularly limited.

The resin formed object of this invention is obtained by ring-openingpolymerization of the polymerizable composition described above.Ring-opening polymerization of the polymerizable composition may beconducted by a bulk polymerization method or a solution polymerizationmethod and preferably conducted by a bulk polymerization method.

The method for obtaining the resin formed object by ring-openingpolymerization of the polymerizable composition of this invention is notparticularly limited, but there are, for example, (a) a method ofapplying the polymerizable composition onto a supporting body andconducting ring-opening polymerization, (b) a method of injecting thepolymerizable composition into a cavity of a forming mold and conductingring-opening polymerization, and (c) a method of impregnating a fiberreinforcement with the polymerizable composition and conductingring-opening polymerization.

Since the polymerizable composition of this invention is low inviscosity, coating in the method (a) can be smoothly performed,injection in the method (b) can be quickly performed throughout thecavity without bubble inclusion even if the cavity has a complicatedshape, and in the method (c) the polymerizable composition can beimpregnated into the fiber reinforcement quickly and uniformly.

According to the method (a), a resin formed object in the shape of afilm, a plate or the like can be obtained. The thickness of the resinformed object is not particularly limited, but is usually 15 mm or less,preferably 10 mm or less and more preferably 5 mm or less.

Examples of the supporting body include films or plates made of resinssuch as polyethylene terephthalate, polypropylene, polyethylene,polycarbonate, polyethylene naphthalate, polyallylate and Nylon; filmsor plates made of metal materials such as iron, stainless steel, copper,aluminum, nickel, chromium, gold and silver. Among them, preferable ismetal foils or resin films. The thickness of the metal foil or the resinfilm is usually in the range of 1 to 150 μm, preferably 2 to 100 μm, andmore preferably 3 to 75 μm from the viewpoint of workability.

Example of the method for applying the polymerizable composition of thisinvention onto the supporting body include known coating methods such asa spray coating method, a dip coating method, a roll coating method, acurtain coating method, a die coating method, and a slit coating method.

The polymerizable composition coated on the supporting body is dried ifnecessary and then ring-opening polymerization is conducted. Thepolymerizable composition is heated to conduct ring-openingpolymerization. Examples of the method for heating the polymerizablecomposition include a method for heating the supporting body placed on aheating plate, a method for heating under a pressure (heat pressing)using a press machine, a method for pressing by using a heated roller,and a method using a heating furnace.

The shape of the resin formed object obtained by the method (b) can beset by the shape of the forming mold, and examples thereof include afilm, a column, and any other three-dimensional shapes.

The shape, material and size of the forming mold are not particularlylimited. Such forming mold includes, for example, conventional knownmolds such as a split mold, that is, a mold having a core mold and acavity mold; and a mold in which spacers are provided between twoplates.

The charging pressure (injection pressure) at which the cavity ischarged with the polymerizable composition of this invention is usually0.01 to 10 MPa, preferably 0.02 to 5 MPa. When the charging pressure istoo low, the injection thereof is insufficient and thus a transfer faceformed on the inner periphery of the cavity tends to be not excellentlytransferred, while when the charging pressure is too high, the rigidityof the mold should be higher, which is not economical. The clampingpressure is usually in the range of 0.01 to 10 MPa.

By heating the polymerizable composition injected in the cavity,ring-opening polymerization can be conducted. Examples of the method forheating the polymerizable composition include a method using a heatingmeans such as an electric heater or steam attached to the forming mold,and a method for heating the forming mold in a electric furnace.

As the resin formed object obtained by the method (c), for example, aprepreg in which the ring-opening polymer is filled into the gap of afiber reinforcement can be cited. As the fiber reinforcement, a fibermade of organic and/or inorganic material can be used and examplesthereof include known fibers such as a glass fiber, a metal fiber, aceramic fiber, a carbon fiber, an aramid fiber, a polyethyleneterephthalate fiber, a vinylon fiber, a polyester fiber, and an amidefiber. These can be used either alone or in combination of two or more.Examples of the shape of the fiber reinforcement include a mat, a clothand a nonwoven fabric.

An example of the method for impregnating the fiber reinforcement withthe polymerizable composition of this invention is a method in which apredetermined amount of the polymerizable composition is poured over thefiber reinforcement such as a cloth or a mat, a protective film is ifnecessary laminated on the wet coated fiber reinforcement, and pressingthe wet coated fiber reinforcement using a roller from the upper side.After impregnating the fiber reinforcement with the polymerizablecomposition, the impregnated product is heated at a predeterminedtemperature to conduct bulk polymerization to obtain the fiberreinforced formed object in which the polymer is impregnated. Examplesof the method for heating the impregnated product are a method ofsetting the impregnated product on the supporting body and heating asthe same manner in the method (a); and a method of setting the fiberreinforcement in the forming mold, then impregnating the fiberreinforcement with the polymerizable composition, and heating as thesame manner in the method (b).

In any of the methods (a), (b) and (c), the heating temperature (in themethod (b), metal mold temperature) for ring-opening polymerization ofthe polymerizable composition is usually in the range of 30 to 250° C.and preferably 50 to 200° C. The polymerization time can be properlyset, and is usually in the range of 10 seconds to 20 minutes andpreferably 30 seconds to 5 minutes.

The polymerizable composition is heated at the predetermined temperatureto thereby start the bulk polymerization reaction. When the bulkpolymerization reaction is started, the temperature of the polymerizablecomposition rapidly rises by reaction heat and reaches a peaktemperature in a short time (for example, 10 seconds to 5 minutes).Although the polymerization reaction keeps on advancing for a while, thepolymerization reaction is gradually settled, and the temperaturethereof goes down. It is preferable to set the peak temperature on thetemperature equal to or higher than the glass transition temperature ofthe resin constituting the resin formed object obtained by thepolymerization reaction since the polymerization reaction progressescompletely. The peak temperature can be controlled by the heatingtemperature. When the resin formed object is obtained by polymerizingthe polymerizable composition containing the chain transfer agent, thepolymerization reaction conversion of the resin formed object is usually80% or more, preferably 90% or more and more preferably 95% or more. Thepolymerization reaction conversion of the resin formed object can bedetermined, for example, by analyzing a solution that is prepared bydissolving the resin formed object in a solvent with a gaschromatography. The resin formed object in which polymerization has beenalmost completely progressed is less in residual monomer and almost freeof a smell originating from the residual monomer.

When the peak temperature during the ring-opening polymerization is toohigh, not only ring-opening polymerization but also crosslinkingreaction may progress. Therefore, in order to progress only ring-openingpolymerization reaction completely without progressing crosslinkingreaction, it is required to control the peak temperature during thering-opening bulk polymerization to be preferably lower than 200° C.

In this case, the peak temperature during the ring-openingpolymerization is preferably equal to or lower than one minute half-lifetemperature of the radical generating agent. Herein, the term “oneminute half-life temperature” means the temperature at which half of theoriginal amount of the radical generating agent decomposes in oneminute. For example, in a case of di-t-butyl peroxide, the temperatureis 186° C. and in a case of 2,5-dimethyl-2,5-di(t-butylperoxy)-hexine-3,the temperature is 194° C.

A crosslinked resin formed object of this invention can be obtained byheating the resin formed object described above. The temperature forheating and crosslinking the resin formed object is usually in the rangeof 170 to 250° C. and preferably 180 to 220° C. This temperature ispreferably higher than the peak temperature during the ring-openingpolymerization and is more preferably higher than the peak temperaturethereof by 20° C. or more. The time for heating and crosslinking theresin formed object is not particularly limited, but is usually in therange of several minutes to several hours.

The method for heating and crosslinking the resin formed object of thisinvention is not particularly limited. When the resin formed object isin the shape of a film, preferably adopted is a method of laminating aplural resin formed objects if necessary and heating the resin formedobject(s) by heat press. The pressure of heat press is usually in therange of 0.5 to 20 MPa and preferably 3 to 10 MPa.

A crosslinked resin composite of this invention is obtained bylaminating the resin formed object of this invention with a basematerial and heating the laminate for crosslinking.

Examples of the base material include metal foils such as a copper foil,an aluminum foil, a nickel foil, a chromium foil, a gold foil and asilver foil; substrates for printed wiring board; and resin films suchas a polytetrafluoroethylene (PTFE) film, a conductive polymer film. Thesurface of the base film may also treated with a silane coupling agent,a thiol coupling agent, a titanate coupling agent, various kinds ofadhesives or the like. When the resin formed object is manufactured bythe above method (a), the supporting body as is may be used as the basematerial.

The crosslinked resin formed object of this invention can also beobtained using the polymerizable composition in a single step (withoutforming the resin formed object). In order to obtain the crosslinkedresin formed object in a single step, it is required to set thetemperature for ring-opening polymerization high and to heat thepolymerizable composition to the temperature at which crosslinkingreaction occurs. However, when the crosslinked resin composite isintended to be manufactured, it is preferable to produce the resinformed object once and thereafter produce the crosslinked resincomposite because peel strength in the interface result in high.Besides, the crosslinked resin composite has an advantage of beingmanufactured in a very simple way since the step of vaporizing thesolvent as is done in a conventional cast method is not necessary.

The heating method for manufacturing the crosslinked resin composite ofthis invention is not particularly limited, but preferable is a methodof laminating the resin formed object with the base material such as themetal foil or the substrate for printed wiring board and then heatpressing the laminate, because the productivity thereof is high. Thecondition for heat pressing the laminate is the same as in producing thecrosslinked resin formed object.

A metal foil clad laminate with a high adherence between the crosslinkedresin and the metal foil can be obtained, for example, by laminating theresin formed object of this invention with the metal foil as the basematerial, and heating and crosslinking by heat pressing. The peelstrength of the metal foil of the metal foil clad laminate obtained,when a copper foil is employed as the metal foil, is preferably 0.8 kN/mor more and more preferably 1.2 kN/m or more, which is measured based onJIS C 6481.

The crosslinked resin formed object and the crosslinked resin compositeobtained by using the polymerizable composition or the resin formedobject of this invention have the same characteristics such as a lowlinear expansion coefficient, a high mechanical strength and a lowdielectric loss tangent and the like as the cycloolefin resin originallyhas, and further are excellent in heat resistance and adherence incomparison to the conventional cycloolefin resin.

The crosslinked resin formed object and the crosslinked resin compositeof this invention with such features are preferably used as electronicpart materials such as a prepreg, a resin laminated copper foil, aprinted wiring board, an insulation sheet, an interlayer insulationfilm, an overcoat and an antenna substrate.

EXAMPLES

The present invention is specifically described by referring examplesand comparative examples. Testing and evaluation in the examples and thecomparative examples are conducted in the following ways:

(1) Weight-Average Molecular Weight (Mw)

A resin portion of the prepreg was dissolved into tetrahydrofuran andthe weight-average molecular weight (Mw) in terms of polystyrene wasmeasured with gel permeation chromatography (GPC) to obtain Mw of thepolymer in the resin formed object.

(2) Glass Transition Temperature (Tg)

Glass transition temperature (° C.) was measured by using the sampleobtained from the resin portion of the single sided copper clad laminatewith differential scanning calorimeter based on JIS C 6481.

(3) Heat Resistance

Heat resistance was measured by floating a resin portion of the singlesided copper clad laminate in a solder bath at 280° C. for 20 secondsaccording to JIS C 6481, and results were evaluated with the followingcriteria.

◯: no swell

Δ: slight swell

X: with a swell

(4) Residual Ratio

Residual ratio was obtained by removing a copper foil of the single sidecopper clad laminate by etching with a ammonium persulfate aqueoussolution, then cutting off the remaining plate into a disc with adiameter of 10 mm, then immersing the disc in toluene at 23° C. for 24hours, then picking up the disc from the toluene, then drying the discwith a vacuum drier at 60° C. for 5 hr, and calculating the ratio(residual ratio) of the weight of the disc after drying relative to theweight of the disc before immersing in toluene. A crosslinked resinformed object with a high residual ratio means that it has a highcrosslinking density.

Example 1

Put into a 30 ml glass bottle were 42 mg of 3,5-di-t-butylhydroxyanisole(antioxidant), 11.3 g (0.04 mole) oftetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene, 3.7 g (0.004 mole) of2-norbornene, 0.45 g of 5-vinyl-2-norbornene, 0.30 g of divinylbenzene(with a purity of 55%, a mixture of m- and p-divinylbenzenes,manufactured by Tokyo Kasei Kogyo Co., Ltd., including ethylbenzene anddiethylbenzene as impurities) and 0.22 ml of di-t-butyl peroxide (oneminute half-life temperature of 186° C.), and 0.06 ml of toluenesolution of benzylidene(1,3-dimesitylimidazolidin-2-ylidene)(tricyclohexylphosphine)rutheniumdichloride with a concentration of 0.05 mol/l further was added into theglass bottle and the mixture was stirred to prepare a polymerizablecomposition.

Two sheets of glass cloths cut off each in size of 200 mm in length×200mm in width, having a thickness of 0.174 mm (a trade No. 7628/AS891AW,manufactured by ASAHI-SHWEBEL CO., LTD.) were placed on a glass fiberreinforced PTFE resin film cut off in size of 300 mm in length and 300mm in width, having a thickness of 0.08 mm (with a product No. 5310,manufactured by SAINT-GOBAIN KK), the polymerizable composition waspoured over the glass cloths. Another sheet of glass fiber reinforcedpolytetrafluoroethylene resin film same as above was placed on the glasscloths, and the laminate was roller pressed to impregnate the glasscloths with the polymerizable composition.

The laminate in which the impregnating glass cloths were sandwichedbetween the glass fiber reinforced PTFE resin films was polymerized byadhering onto a hot plate heated at 145° C. for 1 minute. Thereafter,the two glass fiber reinforced PTFE resin films were both peeled offfrom the upper and lower surface of the laminate to obtain a prepreg,which was a resin formed object.

One drop of acetic acid was added into 60 g of distilled water in aglass vessel and further 0.18 g of styryltrimethoxysilane (KEM-1403,manufactured by Shin-Etsu Chemical Co., Ltd.) was added therein, andstirring the mixture for 1 hour for hydrolysis and dissolution to obtaina silane coupling agent solution. The silane coupling agent solutionobtained was coated, by using an absorbent cotton, on a rough surface ofan electrodeposited copper foil (a rough surface GTS treated product,manufactured by FURUKAWA CIRCUIT FOIL Co., Ltd.) with a thickness of0.018 mm, and followed by drying in a nitrogen atmosphere at 130° C. for1 hour.

Three sheets of samples each sheet was cut off in size of 87 mm inlength×87 mm in width from the prepreg were laminated one another andsandwiched between the electrodeposited copper foil (the rough surfaceof which was in contact with the prepreg) and a PTFE film having athickness of 0.05 mm. In this state the laminate was put into a mold inthe shape of framed rectangle, in inner size of 90 mm in length and 90mm in width and with a thickness of 1 mm, and the laminate was heatpressed in the mold frame under a press pressure of 4.1 MPa at 200° C.for 15 min. Thereafter, the laminate was cooled down while the presspressure was kept on, and the sample was taken off after the temperaturethereof was at 100° C. or less to obtain a double sided copper cladlaminate, which was a crosslinked resin composite.

In Table 1, there are shown a weight-average molecular weight (Mw) ofthe polymer in the prepreg, and the glass transition temperature (Tg)and evaluation results of heat resistance and the residual ratio of thecrosslinked resin in the crosslinked resin formed object constitutingthe single side copper clad laminate.

Example 2

Example 2 was conducted in the same manner as in Example 1 with theexception that the amount of 5-vinyl-2-norbornene was changed to 0.75 g(0.0625 mol). The test same as in Example 1 was conducted, results ofwhich are shown in Table 1.

Comparative Example 1

Comparative Example 1 was conducted in the same manner as in Example 1with the exception that 5-vinyl-2-norbornene was not added. The testsame as in Example 1 was conducted, results of which are shown in Table1.

TABLE 1 Specific cycloolefin Crosslinked resin 5-vinyl-2- complexmaterial norbornene Prepreg Tg Heat Residual (mole %) Mw (° C.)resistance ratio(%) Example 1 3.3 30,500 112 ◯ 91 Example 2 4.7 29,600109 ◯ 94 Comparative 0 29,800 114 X 85 Example 1

As shown in Table 1, the crosslinked resin formed object constitutingthe single side copper clad laminate, which was the crosslinkable resincomposite obtained using the polymerizable composition of thisinvention, was excellent in heat resistance. It is found that thecrosslinked resin formed objects obtained are crosslinked products ofthe thermoplastic resin because each of them has the glass transitionpoint. It is also found that the crosslinked resin formed objectsobtained have a high crosslinking density because the residual ratiosthereof are high (Examples 1 and 2).

On the other hand, the crosslinked resin formed object constituting thecrosslinked resin composite and obtained by using the polymerizablecomposition into which the cycloolefin having, as a substituent group, amonovalent group including a carbon-carbon unsaturated bond (specificcycloolefin) was not added was poor in heat resistance. It is found thatthe crosslinked resin formed object is low in crosslinking densitybecause the residual ratio thereof is high (Comparative Example 1).

1. A polymerizable composition comprising: a cycloolefin mixturecontaining 0.1 to 50% by mole of a cycloolefin having, as a substituentgroup, a monovalent group including an aliphatic carbon-carbonunsaturated bond, a metathesis polymerization catalyst, a radicalgenerating agent, and a chain transfer acent.
 2. A resin formed objectobtained by ring-opening polymerizing the polymerizable composition asclaimed in claim
 1. 3. A resin formed object obtained by applying thepolymerizable composition as claimed in claim 1 on a supporting body,followed by ring-opening polymerizing the polymerizable compositionapplied.
 4. A resin formed object obtained by injecting thepolymerizable composition as chimed in claim 1 into a cavity of mold,followed by ring-opening polymerizing the polymerizable compositioninjected.
 5. A resin formed object obtained by impregnating a fiberreinforcement with the polymerizable composition as claimed in claim 1,followed by ring-opening polymerizing the polymerizable compositionimpregnated.
 6. A crosslinked resin formed object obtained by heatingand crosslinking the resin formed object as claimed in claim 2 to thetemperature higher than the peak temperature during the ring-openingpolymerization.
 7. A crosslinked resin composite obtained by laminatingthe resin formed object as claimed in claim 2 with a base material,followed by heating and crosslinking the laminate.
 8. A polymerizablecomposition comprising: a cycloolefin mixture containing 0.1 to 50% bymole of a cycloolefin having, as a substituent group, a monovalent groupincluding an aliphatic carbon-carbon unsaturated bond at the terminal ofthe monovalent group, a metathesis polymerization catalyst, a radicalgenerating agent, and a chain transfer agent.
 9. The polymerizablecomposition according to claim 8, wherein the monovalent group is atleast one selected from the group consisting of vinyl group, allylgroup, acryloyl group, methacryloyl group, vinyloxy group, allyloxygroup, vinyloxycarbonyl group, allyloxycarbonyl group, acryloxymethylgroup, methacryloxymethyl group, vinylphenyl group and2-propenoxycarbonylphenyloxycarbonyl group.
 10. The polymerizablecomposition according to claim 8, wherein the monovalent group is atleast one selected from the group consisting of vinyl group and allylgroup.